CN114197071A

CN114197071A - Heat-storage warm-keeping antistatic acrylic fiber blending spinning solution

Info

Publication number: CN114197071A
Application number: CN202111583543.7A
Authority: CN
Inventors: 马正升; 董红霞; 赵亮东; 马逸凡
Original assignee: Shanghai Guofan Chemical New Material Co ltd
Current assignee: Shanghai Guofan Chemical New Material Co ltd
Priority date: 2021-12-22
Filing date: 2021-12-22
Publication date: 2022-03-18
Anticipated expiration: 2041-12-22
Also published as: CN114197071B

Abstract

The application provides a heat-storage warm-keeping antistatic acrylic fiber composition and a heat-storage warm-keeping antistatic acrylic fiber blending spinning solution, which comprise acrylic fibers, an inorganic modifier, an organic modifier and a solvent, wherein the organic modifier is a polymer, and the inorganic modifier at least comprises nanoparticles. In the blending spinning process, the inorganic modifier and the organic modifier can be enriched on the outer layer of the acrylic fiber to form the acrylic fiber with a skin-core structure, so that a better modification effect is obtained, and the durability is very good; meanwhile, the spinning performance of the acrylic fiber is not influenced.

Description

Heat-storage warm-keeping antistatic acrylic fiber blending spinning solution

Technical Field

The invention relates to the technical field of acrylic fiber modification, in particular to acrylic fiber with heat storage, heat preservation and antistatic properties.

Background

Acrylic fiber (polyacrylonitrile fiber) is one of important varieties in chemical fiber, and is widely applied to the textile fields of textiles, clothing, automobile seats, household curtains and the like. Acrylic fibers have the characteristics of wool, such as: good fluffiness and heat retention, and soft hand feeling, so it is called artificial wool or synthetic wool. But the elasticity, strength and heat retention of the acrylic fiber are better than those of the wool, the density of the acrylic fiber is lower than that of the wool, and the sun-proof performance of the acrylic fiber is excellent.

With the continuous upgrade of consumption, consumers put forward higher performance requirements on products such as acrylic fibers and the like. Acrylic fibers have wool bulkiness in hand feeling, but are insufficient in heat storage and warmth retention properties and antistatic properties.

Chinese invention patent CN110424078A discloses a light absorption and heat generation blended yarn, which is prepared by 20-30% of cotton fiber, 30-40% of nano heat generation acrylic fiber blended staple fiber, 15-25% of polyester hollow fiber and 5-35% of spandex fiber, wherein the preparation process of the nano heat generation acrylic fiber blended staple fiber is as follows: firstly, short fibers are prepared by blending nano ceramic particles, nano volcanic rock powder and acrylic fiber spinning solution, and then the fibers are blended with cotton fibers and polypropylene fibers to obtain the nano ceramic acrylic fiber blended short fibers.

Chinese invention patent CN104605717B discloses a moisture-absorbing and heating floor mat and a production method thereof, which comprises the steps of firstly blending moisture-absorbing and heating fibers and acrylic fibers into yarn, then using the yarn as wool yarn by a Raschel warp knitting machine, using polyester yarn as ground yarn to prepare pile fabric, and obtaining a floor mat product with a lasting moisture-absorbing and heating function by specific dyeing and finishing, brushing, ironing and polishing, ironing and shearing, composite process treatment and packaging. The floor mat can be perfectly combined with other floor decoration materials, so that people can obtain more comfortable feeling and healthier experience when moving on the bare feet indoors.

The Chinese invention patent CN111876888A discloses a heat-storage luminous thermal knitted fabric, which comprises an inner layer, a functional acrylic fiber layer and a luminous layer from inside to outside in sequence, wherein the inner layer and the functional acrylic fiber layer are interwoven together through tucking to form a double-layer structure, and the luminous layer is woven and fixed on the functional acrylic fiber layer in a knitting mode; and the luminous coating layer is coated on the surface of the luminous layer. The functional acrylic fiber layer is woven by one or two of far infrared functional acrylic fiber and heat storage and insulation functional acrylic fiber.

Chinese patent CN107779973A discloses an antistatic antibacterial acrylic fiber and a preparation method thereof, wherein a base material polyacrylonitrile dry powder is mixed with an antistatic agent, an antibacterial agent, a pore-forming agent, a synergist and a solvent, then the mixture is heated at a certain dissolving temperature to form a spinning solution, the spinning solution is spun into the acrylic fiber through melt-blown spinning in the air, and the obtained fiber is washed with water and dried to finally obtain the acrylic fiber with the antistatic and antibacterial functions. The main technical characteristic is that pore-forming agent and synergist are added into spinning solution mainly composed of polyacrylonitrile, solvent, antistatic agent and antibacterial agent. Due to the existence of the pore-foaming agent, the hygroscopicity of the fiber is enhanced, and the antistatic property of the fiber is beneficial; the synergistic agent solves the problem of poor compatibility of the antistatic agent and the antibacterial agent with the polyacrylonitrile stock solution, so that the antistatic and antibacterial properties are greatly improved compared with the properties of the antistatic agent and the antibacterial agent which are singly added, and the physical and mechanical properties of the fiber are not greatly influenced.

From the above publications, it can be seen that, in the existing technology for improving the light absorption, heat generation and antistatic performance of acrylic fibers, functional powder materials such as volcanic rock powder, ceramic powder, antistatic agent, etc. are added into an acrylic fiber spinning solution for blending spinning, and in order to ensure the performance effect of products, the addition amount of the modifying components is often relatively high, which leads to the decrease of spinnability of acrylic fibers.

Disclosure of Invention

The application provides acrylic fibers, in particular to thermal storage, warm keeping and antistatic acrylic fibers and an acrylic fiber spinning solution.

The heat-storage warm-keeping antistatic acrylic fiber blending spinning solution comprises acrylic fibers, an inorganic modifier, an organic modifier and a solvent, wherein the organic modifier is a polymer, and the inorganic modifier at least comprises nanoparticles.

The application also provides a heat-storage warm-keeping antistatic acrylic fiber composition which comprises acrylic fibers, an inorganic modifier and an organic modifier, wherein the organic modifier is a polymer, and the inorganic modifier at least comprises nanoparticles.

In a preferred embodiment, the acrylic fibers may be a mixture of polyacrylonitrile and other known spinnable fibers, more preferably, the polyacrylonitrile content in the acrylic fibers is at least 85 wt%, preferably at least 90 wt%.

In a preferred embodiment, the number average molecular weight of the acrylon is preferably 2 to 10 ten thousand.

In a preferred embodiment, the weight ratio of the acrylon to the solvent is preferably 10-50: 50-90, more preferably 15-35: 65-85.

In a preferred embodiment, the solvent is any one or more of aqueous sodium thiocyanate solution, dimethylacetamide, dimethylsulfoxide, N-dimethylformamide, N-methylmorpholine, dimethylamine, an ionic liquid, or nitric acid.

In a preferred embodiment, the acrylic fibers and the solvent form an acrylic fiber spinning solution, and the kinetic viscosity of the acrylic fiber spinning solution is preferably 1-50 Pa.S, more preferably 5-45 Pa.S, and more preferably 10-40 Pa.S.

In a preferred embodiment, the mass concentration of the solvent in the acrylic spinning solution is preferably 50 to 90%, more preferably 65 to 85%.

In a preferred embodiment, the inorganic modifier comprises at least a powder of a copper compound selected from: copper ferrite, tungsten cesium bronze, cuprous sulfide, cuprous chloride, cuprous oxide.

In a preferred embodiment, the average particle size, or the total particle size, of the copper compound powder is between 40 and 200nm, more preferably between 50 and 180nm, and even more preferably between 80 and 150 nm.

In a preferred embodiment, the inorganic modifier may further include silica powder.

In a preferred embodiment, the average particle size or the total particle size of the silica powder is 50 to 150nm, more preferably 80 to 100 nm.

In a preferred embodiment, in the inorganic modifier, the weight ratio of the silica powder is preferably 1-10%.

In a preferred embodiment, the inorganic modifier preferably contains 90-99% by weight of the powder of the copper compound.

In a preferred embodiment, the organic modifier is polyethylene glycol.

In a preferred embodiment, the number average molecular weight of the polyethylene glycol is preferably 5000-.

In a preferred embodiment, the polyethylene glycol has a molecular weight distribution coefficient of 2.0 to 4.0.

In a preferred embodiment, the weight ratio of the organic modifier to the inorganic modifier is 5-100: 1-20.

In a preferred embodiment, the organic modifier and the inorganic modifier form a slurry acrylic modifier.

In a preferred embodiment, the dynamic viscosity of the pulp-like acrylic modifier is preferably not more than 100 mPas, preferably 15 to 50 mPas.

In a preferred embodiment, the preparation method of the sizing acrylic fiber modifier comprises the following steps: and mixing and pulping the inorganic modifier and the organic modifier to prepare the slurry acrylic modifier.

In a preferred embodiment, the mixing and beating process is carried out in a blender, preferably at a rate of 10-30 rpm.

In a preferred embodiment, the temperature is kept between 30 and 60 ℃ during the mixing and beating process.

In a preferred embodiment, the mixing time during the mixing and beating process is at least 0.5h, more preferably 0.5-1 h.

The heat-storage warm-keeping antistatic acrylic fiber can realize the utilization of photothermal conversion of the area with 400 plus 760nm with most concentrated solar energy on one hand, and can realize the efficient reflection of far infrared wavelength emitted by a human body to play a role in heat storage and warm keeping.

According to the heat-storage warm-keeping antistatic acrylic fiber, the organic modifier plays a role in dispersing the inorganic nano modifier, the organic modifier is macromolecular, the inorganic modifier is coated and dispersed, and the problem of agglomeration of the inorganic modifier is greatly reduced. The spinning performance of the acrylic fiber is not affected.

The heat-storage warm-keeping antistatic acrylic fiber, the inorganic modifier and the organic modifier can be enriched on the outer layer of the acrylic fiber to form the acrylic fiber with the sheath-core structure, so that a better modification effect is obtained, and the durability is very good. Meanwhile, the spinning performance of the acrylic fiber is not influenced.

Drawings

FIG. 1 is an electron micrograph of a cross section of a "sheath-core structure" fiber obtained in the present application.

Detailed Description

Example 1

In this example, the acrylic modifier comprises:

0.05kg of silicon dioxide powder with the particle size of 80-120 nm;

cuprous sulfide powder with particle size of 100-150nm and 0.95kg

Polyethylene glycol with the number average molecular weight of 12000g/mol and the molecular weight distribution coefficient of 2.2; 2 kg;

the materials are stirred and mixed, the stirring speed is 20rpm, the stirring time is 30min, and the temperature is 35 ℃. The dynamic viscosity of the resulting slurry was 23 mPaS.

In this example, 100kg of acrylic fiber spinning solution, dimethyl sulfoxide as a solvent, 70 mass% of the solvent, and 23Pa · S of dynamic viscosity of the spinning solution were used. The number average molecular weight of the acrylic fiber is 1.5 ten thousand, and the content of the polyacrylonitrile is 100 wt%.

The acrylic fiber modifier and the acrylic fiber spinning solution are blended and spun, and the spinning speed is 10 m/s. And (3) extruding by a spinneret, passing through a coagulating bath consisting of water and dimethyl sulfoxide, and then stretching and heat-setting to obtain the acrylic fiber.

Example 2

In this example, the acrylic modifier comprises:

0.1kg of silicon dioxide powder with the particle size of 80-120 nm;

tungsten cesium bronze powder with particle size of 50-80nm and 0.9kg

Polyethylene glycol with the number average molecular weight of 30000g/mol and the molecular weight distribution coefficient of 3.6; 5 kg;

the materials are stirred and mixed, the stirring speed is 20rpm, the stirring time is 30min, and the temperature is 35 ℃. The dynamic viscosity of the resulting slurry was 24 mPaS.

In this example, 100kg of acrylic fiber spinning solution, dimethyl sulfoxide as a solvent, 70 mass% of the solvent, and 25Pa · S of dynamic viscosity of the spinning solution were used. The number average molecular weight of the acrylic fiber is 3 ten thousand, and the content of the polyacrylonitrile is 100 wt%.

Example 3

In this example, the acrylic modifier comprises:

0.08kg of silicon dioxide powder with the particle size of 50-90 nm;

cuprous chloride powder with particle size of 100-130nm and 0.92kg

Polyethylene glycol with the number average molecular weight of 38000g/mol and the molecular weight distribution coefficient of 2.8; 8 kg;

the materials are stirred and mixed, the stirring speed is 20rpm, the stirring time is 30min, and the temperature is 35 ℃. The dynamic viscosity of the resulting slurry was 16 mPaS.

Example 4

In this example, the acrylic modifier comprises:

silica powder with the particle size of 120-150nm and 0.1 kg;

cuprous oxide powder with particle size of 100-150nm and 1.4kg

Polyethylene glycol with the number average molecular weight of 26000g/mol and the molecular weight distribution coefficient of 2.7; 3 kg;

the materials are stirred and mixed, the stirring speed is 20rpm, the stirring time is 30min, and the temperature is 35 ℃. The dynamic viscosity of the obtained slurry was 35 mPaS

In this example, 100kg of acrylic fiber dope was obtained by dissolving dimethylformamide in a solvent at a concentration of 70% by mass, and the dope had a dynamic viscosity of 27Pa · S. The number average molecular weight of the acrylic fiber is 1.5 ten thousand, the content of polyacrylonitrile is 93 wt% (the content of acrylonitrile monomer), and the balance is vinyl acetate monomer units.

Example 5

In this example, the acrylic modifier comprises:

0.15kg of silicon dioxide powder with the particle size of 70-100 nm;

the particle size of the copper ferrite powder is 120-180nm, and the weight of the copper ferrite powder is 1.85kg

Polyethylene glycol with the number average molecular weight of 38000g/mol and the molecular weight distribution coefficient of 3.3; 1 kg;

the materials are stirred and mixed, the stirring speed is 20rpm, the stirring time is 30min, and the temperature is 35 ℃. The dynamic viscosity of the obtained slurry was 33 mPaS

In this example, 100kg of acrylic fiber spinning solution, dimethyl sulfoxide as a solvent, 70 mass% of the solvent, and 23Pa · S of dynamic viscosity of the spinning solution were used. The number average molecular weight of the acrylic fiber was 1.5 ten thousand, and the polyacrylonitrile content was 100 wt% (acrylonitrile monomer content).

Comparative example 1

In this example, the acrylic modifier comprises:

cuprous oxide powder with particle size of 120-180nm and 2kg

Polyethylene glycol with the number average molecular weight of 38000g/mol and the molecular weight distribution coefficient of 3.3; 4 kg;

Comparative example 2

In this example, the acrylic fiber modifier was:

0.15kg of silicon dioxide powder with the particle size of 70-100 nm;

cuprous oxide powder with particle size of 120-180nm and 1.85kg

In this example, 100kg of acrylic fiber spinning solution, dimethyl sulfoxide as a solvent, 70 mass% of the solvent, and 20Pa · S of dynamic viscosity of the spinning solution were used. The number average molecular weight of the acrylic fiber was 1.5 ten thousand, and the polyacrylonitrile content was 100 wt% (acrylonitrile monomer content).

Comparative example 3

In this example, the acrylic fiber modifier was: polyethylene glycol with the number average molecular weight of 38000g/mol and the molecular weight distribution coefficient of 3.3; 4 kg.

The application takes acrylic fiber spinning solution (dynamic viscosity of the spinning solution is 23 Pa.S, the number average molecular weight of acrylic fiber is 1.5 ten thousand, and the content of polyacrylonitrile is 100 wt%) with the same specification without adding inorganic modifier and organic modifier as a reference, and the experimental results obtained in the above examples and comparative examples are shown in the following table 1.

TABLE 1, Experimental results obtained in examples 1-5 and comparative examples 1-3

The fiber temperature rise test method comprises the following steps: placing acrylic fiber at 20-100mW/cm²The fiber temperature after 30min of irradiation was measured at the illumination intensity.

The acrylic fiber modifier can realize good modification effect under the condition of small addition amount (less than or equal to 2 wt%), and meanwhile, the spinning performance of acrylic fibers is hardly influenced.

In comparative example 2, the nano inorganic powder has poor dispersibility in acrylic fibers to form agglomeration without using polyethylene glycol, the acrylic fibers prepared by spinning have stress concentration due to uneven dispersion of the powder in the fibers, the mechanical strength of the fibers is remarkably reduced, and the breaking strength of the fibers is less than 2.0cN/dtex, so that the acrylic fibers have almost no use value. The results show that in the blending modifier composed of the organic modifier and the inorganic modifier, the organic modifier plays a role in dispersing the inorganic nano modifier, the organic modifier is macromolecular, the coating and dispersing effects are played on the inorganic modifier, and the problem of agglomeration of the inorganic modifier is greatly reduced.

In comparison with the examples of the present application, in comparative example 1, in the case where nano silica was not used, the fiber heat retaining property and heat storage property were lowered.

Referring to fig. 1, in the co-spinning solution of the present application, in the co-spinning process, an inorganic modifier and an organic modifier diffuse and concentrate on the surface of a fiber. After hot stretch setting, a stable "skin-core structure" is formed, as shown in fig. 1.

The embodiments of the present invention have been described in detail, but the present invention is only by way of example and is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, it is intended that all equivalent alterations and modifications be included within the invention, without departing from the spirit and scope of the invention.

Claims

1. The heat-storage warm-keeping antistatic acrylic fiber blending spinning solution is characterized by comprising acrylic fibers, an inorganic modifier, an organic modifier and a solvent, wherein the organic modifier is a polymer, and the inorganic modifier at least comprises nanoparticles.

2. The thermal storage and insulation antistatic acrylic fiber blending spinning solution as claimed in claim 1, wherein the acrylic fiber contains polyacrylonitrile at least 85 wt%; the number average molecular weight is 2-10 ten thousand; the weight ratio of the acrylon to the solvent is 10-50: 50-90.

3. The thermal storage and thermal insulation antistatic acrylic fiber blending spinning solution as claimed in claim 1, wherein the solvent is any one or more of sodium thiocyanate aqueous solution, dimethylacetamide, dimethylsulfoxide, N-dimethylformamide, N-methylmorpholine, dimethylamine, ionic liquid or nitric acid.

4. The thermal storage and warm keeping antistatic acrylic fiber blending spinning solution as claimed in any one of claims 1 to 3, characterized in that the acrylic fibers and the solvent form an acrylic fiber spinning solution, and the mass concentration of the solvent in the acrylic fiber spinning solution is 50-90%; the dynamic viscosity is 1-50 Pa.S.

5. The thermal storage and insulation antistatic acrylic fiber blending spinning solution as claimed in claim 1, wherein the inorganic modifier at least comprises copper compound powder, and the copper compound is selected from the group consisting of: one or more of copper ferrite, tungsten cesium bronze, cuprous sulfide, cuprous chloride, and cuprous oxide; the average particle diameter or the total particle diameter of the copper compound powder is 40-200 nm.

6. The thermal storage and thermal insulation antistatic acrylic fiber blending spinning solution as claimed in claim 5, wherein the inorganic modifier further comprises silica powder, and the average particle size or the whole particle size of the silica powder is 50-150 nm;

in the inorganic modifier, the weight proportion of silicon dioxide powder is preferably 1-10%; the weight ratio of the copper compound powder is preferably 90 to 99%.

7. The heat-storage warm-keeping antistatic acrylic fiber blending spinning solution as claimed in claim 1, wherein the organic modifier is polyethylene glycol, the number average molecular weight of the polyethylene glycol is 5000-50000g/mol, and the molecular weight distribution coefficient is 2.0-4.0.

8. The thermal storage and warming antistatic acrylic fiber blend spinning solution as claimed in claim 1, wherein the weight ratio of the organic modifier to the inorganic modifier is 5-100: 1-20.

9. The thermal storage and insulation antistatic acrylic fiber blending spinning solution as claimed in claim 1, wherein the organic modifier and the inorganic modifier form a slurry acrylic fiber modifier, and the dynamic viscosity of the slurry acrylic fiber modifier is not more than 100 mPa.S;

the preparation method of the sizing acrylic fiber modifier comprises the following steps: mixing and pulping an inorganic modifier and an organic modifier to prepare the slurry acrylic modifier; wherein the mixing and pulping process is carried out in a stirrer, the stirring speed is 10-30rpm, the temperature is kept at 30-60 ℃, and the mixing time is at least 0.5 h.

10. The heat-storage heat-preservation antistatic acrylic fiber composition used for the blended spinning solution of claim 1 comprises acrylic fibers, an inorganic modifier and an organic modifier, wherein the organic modifier is a polymer, and the inorganic modifier at least comprises nanoparticles.